JPS59133561A - Liquid developer for electrostatic image development - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a carrier α-form with sieve electrical resistivity and low dielectric constant, consisting of a dye, an N-vinylpyrrolidone-containing polymer, a waxy substance and a conventional silkworm egg mixture. The present invention relates to a liquid developer containing negatively charged toner particles for producing a static phenomenon, and a method for producing the same.

This type of liquid material is conveniently used in electrography or xerography to give visibility to electrophotography. In principle, these developers consist of colored particles dispersed in a carrier liquid, in combination with a binder and a charge control agent, if necessary together with a dispersant. The colored particles together with the charge control agent and the attached bond 11 are precipitated electrophoretically within the electric field of the band. The dispersant, binder and charge control agent may be the same.

From the specification of West German Special Application No. 2740870 (corresponding to U.S. Patent No. 4243736), the father has a European patent,
From Japanese Patent Publication No. 0037475, an amount of wax corresponding to the proportion of pigment in a liquid working agent containing an N-vinylpyrrolidone-containing polymer as a binder and a bulking agent and at the same time as a load-adjusting agent is added. It is known to use. This wax has the role of improving the settling properties of the liquid formulation and the wiping resistance of the coating. Polyethylene wax is the wax used. Low-occurrence paraffinized paraffins can also be present. However, fullshade area
eas) is made visible by this hostile developer, but this still does not meet the highest demands (j).

In another printing book 9: 1, it is proposed to add wax to the paper. For example, the technology for cutting the Xian Shu Gen1 was published in West German Patent Application No. 2,532,282 (U.S. Patent No. 39).
92642), which additionally contains polyethylene, polyethylene wax and/or paraffin wax with a softening point of 60 DEG -130 DEG C. By means of this additive mixture, the stability of the liquid state, the precipitation and the viscosity, the gloss and wiping resistance of the copies produced, and the soiling of the equipment are influenced. West German Patent Appearance No. 2538581 (U.S. Patent No. 40
No. 81391 (target) and West German Patent Application Publication (corresponding to U.S. Pat. No. 4,250,241) also contain an electrophotographic film which additionally contains a wax or a polyolefin having a softening point of 60 to 130°C. The embroidery and shading are described. The specific gravity of this m 7J[l mixture is the same as that of the carrier liquid. These are tiJ fj4 during heating liquid state 1 cutting and during cooling phase (7
), it separates in the form of small particles.

West German Patent Application Publication No. 3046654 (US LiW
Forgive me! 4306009) Mei 1411 The cage has 1
Ingredients for shellfish include IJ [1 and special delatex (gel)]
, at; ex) and may contain wax and rosin.

However, the experiments in that specification showed that only polyethylene wax or paraffin wax and beeswax were used, such as polyethylene with a softening point of 115'G and a molecular weight of 1500; Polyethylene and softening point range 60-110
It is shown that paraffin waxes with 0 and It shows a uniformly inked letter and full shading r area, which is a particular drawback when using copy paper with a low surface flatness/lf note.

(8) It is therefore an object of the present invention to produce copies which exhibit good surface area even when using copy paper with low surface smoothness, by electrographic or electrophotographic copying methods, with the known advantageous customization. The purpose is to remove the resulting liquid liquid agent.

This objective was achieved using a developer of the Suimei wholesale type, which had a soft f-point of 50-120°C and an acid temperature of 1++ho to about 200, and had an increased It is necessary to contain at least 1 rJf of wax in the carrier body at a temperature that is easy to bathe, but when viewed indoors, to reduce the electrical conductivity of the liquid iron field.

Waxes which are advantageously used are those which reduce the conductivity of the solids by at least 15% when adding 1M wax to a toner concentrate having a solids content of about 7%.

The liquid developing agent of the present invention advantageously contains from 0.1 to 1.5 parts by weight of wax per part of fine material or dye in the dye. This ensures that copies of better quality can be printed in conventional copiers than those obtained using conventional liquid imaging agents. Full-shade chain acids are more strongly (and more evenly) dusted. Even small grains are accurately reproduced on copy paper with a rough surface. With the use of the present deterioration agent, You can use a cheap copy of copy paper in a very short amount of time.

The reason for this achievement of young fruit is unknown. However, by adding the wax of the present invention, the charge level of the toner particles is lowered, so that the magnetized toner and wax particles are precipitated onto the fk+ layer, which is substantially less sensitive. A large number of toner particles can be easily transferred to copy paper. In addition, the wet, still fixed wax contained in the liquid may be melted during one part of the fixing step and/or re-drunked into the remaining toner liquid. Conceivable. In this case, the unrestricted swimming area is made uniform.

The wax that can be used in accordance with the present invention is characterized by its bathing degree (difficult to understand in a single product of about 95% or more), melting point or softening point range, and toner particle's liquid state. Requirements regarding customization to reduce the conductivity of the agent /1iIi
It is something that helps. Many of these are commercially available. These include acid waxes or ester waxes produced on the basis of Monokun wax. Waxy materials such as hydrated castor oil or polyoctadecene are also suitable. These waxes have a European temperature of 70 to 90°C. The acid value of these waxes is 0 to f
It fluctuates between 1200, but between 0 and 1600 is the best value. Good results are also achieved with distances of 110 to 160. Mixtures of several waxes or mixtures of waxes with polyethylene or paraffin waxes can also be used.

Waxes, for example, have a softening point of 82-88°C and an acid + [1
j 78-88 and saponification ill! Ester wax (1) with 1120-165, soft 1 hit point 76-82°C
, an ester wax (2) with an acidity of 12-20 and a saponification of 125-155 and a softening point of 78-84"O,
and acid wax (3) having an acid number of 165 to 155. Hydrated castor oil (4) with a softening point of 86-88°C and an acid value of 2 is also suitable (11). The following table shows an example of wax for the song for 1 history.

Table 1 5 Oxidized wax 81-37 115-1
606 Dried wax 78-84 115
~1607 Ester wax 79~85 1
5-208 Ester wax 78-86 1
5~309 Ester wax 86~8985~
9510 Ester wax 79-8525-6
511 Hydrated castor oil 83-86 1.
512 Water phase castor oil 86-88616
Polyoctadecene 700 1% of the wax of the present invention
When a toner having a solids content of about 7% by weight is cooled, the 2S current efficiency of the liquid IM agent being applied is reduced by at least 15%. This reduction in the toner's charge level is a measure of the reduction in the charge level of the toner. (12) The conductivity reducing effect of the wax can be measured as follows: Liquid aliphatic with a center point of 170-190'O A hot bath solution containing 2.5 I of wax in 6 Q ml of hydrocarbon is stirred into the toner wire 250 I described in Comparative Example 2. The mixture was left to stand for about 24 hours, then treated with aliphatic hydrocarbon 2e, and the conductivity of the mixture thus prepared and ready for use was determined, d, c, in the wax-added mixture in a measuring cell. [611] under the same conditions as in the liquid current iron without the addition of 611]. 1 obtained using the wax of the present invention
The directivity is shown in Table 2 below.

Table 2 Suitable carrier dispersions are, in particular, the known single-sided hydrocarbons having a boiling point of 150 to 190°C, which are commonly used in liquid carriers. The examples described here (and these are not intended to limit the invention) are petroleum fractions, which are essentially odorless, relatively pure, and not available on the market. Ru. These products include various hydrocarbon mixtures having about 8 to 16 carbon atoms. This has a higher nausea resistance than 109 ohms and approximately 6
What is the lower duck army rate?

This developer liquid should be able to evaporate sufficiently quickly at a lower evaporation temperature than the temperature at which the copy paper is inked. Advantageously, this current IN 71J solution does not contain aromatic notes or unusual toxic notes or other ingredients that have a corrosive effect. Furthermore, this developer g1+ has a viscosity low enough to prevent the rapid movement of particles attracted by the electrostatically electrified blank area to be agitated.

The viscosity of the carrier liquid is between 0.5 and 2.5 mPa.
.

It varies between S.

(1b) The pigments used in the present invention are known. Typically, a synthetic car 444 gun black is used to make black paint + & MIJ444. For coloring, for example, add back color pigment to curl. It is possible to separate in black.

In principle, all organic and inorganic pigments and dyes can be used. Examples of these are: carbon black (C,1,/1677266), oil blue (C,1,,1661555), alkali blue (C,1,/1642750), phthalocyanine blue (C, 1, Whistle 74160), Phthalonanine Green (C, 1, A674260 or 42040), Spirit Black (C8I, N, 50415 L
Oil Violet (C, 1, %, 6U725)
, Benjicine Yellow (C-1, Iku, 21090 or 21100), Methyl Orange (C0■, 1602
5), Brilliant Carmine (C, 1,, whistle, 15
85 [J) or First Red (C, 1,%, 15
81ri5).

Contains N-vinylpyrrolidone and is a common drug of the KomailVj family (16
) A neutral polymer is used to create a negative charge on the pigment particles. These include a copolymer consisting of 215 to 40% of N-vinylpyrrolidone and a methacrylic acid ester having a carbon alkyl group having 6 or more carbon atoms, or an n-
Vinylpyrrolidone-22.5-10% by weight grafted 1
- Also included are graft polymers and copolymers of methacrylic acid esters.

Other known negative tone permutations Y11 are skin scars, lecithin or 1 fat-containing compound C, of course, some sulfonic acid salts, and sodium dioctyl-sulfosuccinates. Salt can also be used. It is also flexible for simultaneous use of several adjustment pieces.

With any small force, you can check the toner characteristics, charge level, precipitate customization, months lifespan, re-release of aggregates FtV4
, transportability and wiping resistance on copy paper may be affected.

Customary weights that can optionally be added are: a) halogen-containing waxes, typically chlorparaffin with a chlorine content of 70%; b) soluble in the carrier liquid. Examples of polymers include styrene/detadiene copolymer, polyvinyl alkyl ester, polyisobutylene, polyvinyl stearate and A
Polyacrylate or polymethacrylate with N-alcohol groups 1, C) 1 ester of CXT bath in the carrier liquid, 1 hydrocarbon 11 and polyterpene 1141 Jid) Of
Plastic ΔIJ toe is phthalate-related dialkyl.

The amount of wax contained in the liquid state 1 station cup due to non-invention fluctuates widely. It is advantageous to apply 0.6 to 0.8 mw% of wax per 1i'ilt% of P, J4 family.

The ratio of purity to polymer and shield color MIJ is not very close. For example, 0.2 to 6 parts of polymer are used per 1 part of #j4 paste or dye.

The invention also relates to a method of making a liquid developer.

When manufacturing a liquid abrasive agent, the wax of the present invention is added to this -! I! ! ! Note that during any of the five stages of the pickling process, the sweetfish is soaked in a carrier liquid by heating; Upon cooling, this wax aggregates to 0.1 to IAi
Ad1 particles or microcrystals carrying dimensions of oμ are suitable.

Generally, wax is added to the door material paste to reduce additional steps in the manufacture of liquid adhesives. For this purpose, a wax scoop or a wax dispersion can be used by dipping the wax into a hot carrier liquid and cooling the bath. While the raw paste is being molded, the #j$ crushed stock should be added 2 times at a time so that the wax is coated.

Gearia fluid with high electrical resistivity and low dielectric constant,
Fine wood or dyes, N-vinylpyrrolidone-containing polymers, waxy substances and the proboscis of ponds produce electrostatic m1 phenomena.
The inventive method of loading a rinsing agent with negatively charged toner particles to represent a pigment or dye in a carrier liquid, an N-vinylpyrrolidone-containing polymer, and (19) ) Form a paste of 110 additives, grind this paste of IQ family in warm water at 60-100°C, and grind this ground v
! By using a carrier liquid that can be used as a polymer containing N-vinylpyrrolidone, the toner concentrate can be deposited and the toner can be filled with 5 to 20 times the amount of carrier liquid. Therefore, this method has a softening t
It is easy to bathe with M degree of 50-120'C and acid with 1 to about 200 degrees of hot water in a carrier liquid. 4) Putting at least one wax that lowers the chance of harm into a paste, a cupboard, or a toner concentrate will make it an enemy.

It is advantageous to add this wax to the raw paste in the form of finely divided solid particles or dispersed in a carrier liquid.

Another method of making this liquid incubator involves adding the wax, in the form of a hot liquid, to the toner concentrate under stirring.

Five-season roller mills, friction mills, ball mills, ball mill agitators, etc. are suitable for dispersing the raw material paste. 4. For the selection of crushed compositions,
Use a propeller mixer, laboratory bath opening neck, or high-speed stirring device.

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Comparative Example 1 a)) Preparation of N-vinyl pyrrolidone (West German patent) Dodecyl methacrylate/methyl methacrylate copolymer (76:20) having a common average molecular weight of about 450,000 (96:20) Commercially available grafted polymer 20% bath solution 200I and boiling point 17.
A paste was prepared consisting of carbon black 60.9, steel phthalocyanine 18.9 in aliphatic hydrocarbon 450 I at 0-190 DEG C. and 24 g of powdered polyethylene wax with an average molecular weight of 1500.

This raw material paste was heated in a ball mill at 80°C for 3 hours, and 20% of the previous graft polymer solution was added.
09 and the hydrocarbon 1900.9.

b) Preparation of liquid developer The toner concentrate produced by the method described in a) is about 9i! of aliphatic hydrocarbons (boiling point 160-180C). produces good copies, has a long useful life, and has a negative load.
A liquid agent containing mixed toner particles was dispensed. However, the Foursiere PVP area was unevenly inked.

Examples 1 to 4 10 g of wax (as described in No. 6) was added to 50 to 8 [J'O at 7 degrees did.

Next, this inkstone was heated with a constant ηδ force of 500ν of Tani toner produced according to Comparative Example 1,
During this time, stir using a laboratory molten device.

Subsequently, this mixture was further mixed with a high-speed stirrer for 2"
/ minutes of stirring.

Add this mixture to FJ 9 times the amount of self-help hydrocarbon (1 point 1
60 to 180"C), and a ready-to-use sample was selected. The results achieved using this material in a conventional copying machine are shown in the sixth section. Compare in table.

(26) Table 6 Example 5 Ester wax (soft fb point 82-88"0) 3
Column 1 comparing 011 and chlorparaffin (Inn sorting 70% 4I) with aliphatic hydrocarbon (astigmatism 170-180 °C)
ON-vinylpyrrolidone copolymer bath dispersion 200.9 m was poured into a mixture of 200.9 mm, and this bath liquid was then quenched. Carbon black 609 and copper phthalocyanine Y18. ! i”
& Added because of the resulting wax dispersion. The raw material paste was ground in the same manner as described in Comparative Example 1, and the copolymer solution 3
(24) 00g and aliphatic hydrocarbon system 1900' to prepare a toner concentrate.

This toner concentrate was then converted to an aliphatic hydrocarbon system (?u% point 1 (So ~ 180''C)) that was 7 times more concentrated to obtain a liquid-state liquid that was ready for use. .It exhibited rich contrast and extremely uniform full shade areas on conventional reproduction equipment.

Usually, 1Mt of dry toner is not suitable for use with liquid toner.
Good copying was also hoped for on the platform using All paper.

The procedure described in Example 5 was repeated, except that an acid wax having a softening point of 78-84°C and an acid temperature of 165-155°C was used.

This toner yield was further agitated using a high speed mixer.

Testing on a copying machine yielded good copies as in Example 5.

Example 7 The method described in Example 5 was repeated using a polyoctadecene with a melt viscosity (140°) of 605 mPa, s, &c.

Using this toner in a conventional copying machine, warm full shade areas were produced even on rough copy paper.

Example 8 Carbon black 601/Copper phthalocyanine 20.9 Chlorparaffin
4g ratio Graft polymer solution with d self-loaded on soft mosa 1 200.9 and 8-molecular aliphatic hydrocarbon (d point 17
A raw material paste consisting of 420.9 (0 to 190°C),
It was crushed in the same manner as described in Rikoku 1+I11. Graft this paste with 300g of polymer solution and $1900 of hydrocarbon water.
．． The toner mixture prepared by diluting the toner with 9 parts was further stirred with a high-speed mixer.

The method suitable for use with conventional copying equipment is 6.
It was prepared by mixing with 5 times the amount of aliphatic hydrocarbon and then tested. I love that there are no copies with full shade areas.

Example 9 Row 8 was repeated using a paste of the following raw materials: Carbon black 60 g Steel phthalocyanine 24.9 Ester wax as described in Example 8 30.9 Chlorparaffin 4 g Copolymer M of Comparative Example 1 200.9 l
1ii aliphatic hydrocarbon accumulation ('fJD point 17tJ ~ 19O-
C) 420.9 After dilution as described in Example 8, a liquid emulsion was poured into a barrel and used in a conventional foam photography brewer. The desired copy showed a hidden uniform area.

Example 10 Carbon Black 6CJ l Steel Phthalocyanine 18.9 (27) Copolymer Bath of Comparative Example 1 A paste of the yA family consisting of 200.9 was ground as described for Softness Reli 1.

This ground material 750I was stirred vigorously in a laboratory dissolver while producing +1ilffl group hydrocarbons (boiling point 1
60-1l80-0) 600 and the copolymer bath solution 21Uj1 of d above was used.

The resulting toner yield contains 6 times as much aliphatic hydrocarbons (boiling point 1
By adding 60 to 180 ''0) and selecting ?#, it was made into a liquid agent that can be used.Even when dry toner copy paper is used with a conventional straw plate, it has poor quality. I loved the copy.

A raw material paste consisting of 200 g (28) of the copolymer m liquid described in Carbon Black 609 Copper Phthalon Aniy 181 Ratio Softening 111 was ground in the same manner as described in Ratio Softening Example 1.

This ground material 1409 was mixed with the copolymer m72!9 of Taniya Example 1 and the aliphatic hydrocarbon (r'lli point 170 ~
190''C) 350.9, followed by
To each of the dissolved mvtt was added a hot solution of 81% of the wax (listed in Table 4) in 75.9% of aliphatic hydrogen ash under vigorous stirring using a laboratory dissolver. It was a festival.

The liquid agent obtained by dilution with 8 cycles of hydrocarbon (boiling point 160-180°C) gave the following results: Table 4 Table 11 (comparison) Polyethylene wax Heterogeneous (softening point 76-82) °C) 20 (relatively soft) Beeswax Unrestricted - Comparative 2 Carbon black 601 Copper phthalocyanine 189 Graft polymer common liquid described in Shio 1 200 A raw material paste consisting of F was ground in the same manner as described in Comparative Example 1.

This crushed material was made into a toner mixture with a mixture of 680 g of the graft polymer bath solution and 11 ml of aliphatic hydrocarbon solution (Soy).

7 times the amount of sour aliphatic hydrocarbons (boiling point 160-180'C)
A liquid phenolic agent was created by dispersing the color, which produced a copy of the unevenly inked full-shade area. 170~190"C)
A bath of 2.5 g of wax in 22.5 g of wax was gradually poured into the toner concentrate 26D9 prepared according to Comparative Example 2, while stirring vigorously using a laboratory Ditzel 7-inch. After 7 JOi, the mixture was stirred for 5 min (61 min).

This ghostly proboscis is an aliphatic hydrocarbon (boiling point 160-18
A ready-to-use liquid preparation was prepared by diluting the drug at 0°C. This liquid state in the performance feeding device 1
The results of the elephant MIJ test are compared in Table 5.

Table 5 (Softening point 119-126°C) 24 Beeswax
Heterogeneity (62) Agent Patent Attorney Yano E Yu.

(1 other person)

Claims (1)

[Claims] 1. Carrier liquid, pigment or dye, N-vinylpyrrolidone-containing polymer wax-like material with high hyporesistivity and low dielectric constant! 1I71 quality and commonly used, this liquid state 1
The elephant agent has a soft f point of 50~120℃, acid + tlfl O~
It is characterized by containing at least 14 layers of wax, which absorbs about 200 ml and is easily dissolved in the carrier liquid when the temperature rises, but is dissolvable in the chamber ml, and reduces the conductivity of the liquid state. A liquid phenolic agent. 2. The wax lowers the electrical conductivity of the liquid developer by at least 15 times compared to adding 1% by weight of wax to a toner concentrate having a solids content of about 7%. *
**The liquid state phenomenon 1 R described in the desired range i4. 6. The wax has a softening point of 70 to 90 "C," the liquid phenomenon according to claim 1. 4. The wax has a softening point of 70 to 90 "C." 4. The wax has a softening point of 70 to 90 "C." , the liquid developer according to claim 1. 5. The liquid developer according to claim 1, wherein the wax has an acid content of 10 to 160. 6. Pigment. Or 0.1 to 1.0% wax per dye #+1 part by weight.
5% by weight of the liquid phenomenon according to claim 1. The Z wax is derived from montan wax, has a softening point of 82 to 88°C, an acid value of 78 to 88 and a -1 [1Ii
is an ester wax having f! from 120 to 165;
A liquid developer according to any one of claims 1 to 6. 8. The wax is derived from montan wax,
Softening point 76-820X acid value 15-20 and saponification value 125
155. The liquid powder according to any one of claims 1 to 6, which is an ester wax having the following properties. 9 The wax is derived from montan wax and has a softening point of 78-86'O, an acid value of 15-60 and a saponification value of 160.
The liquid developer according to any one of claims 1 to 6, which is an ester wax having a formula of 150 to 150. 10. The wax is N4 made from Montan wax.
The liquid developer according to any one of claims 1 to 6, which is an acid wax having a softening point of 78 to 84°C and an acid value of 165 to 155. 11. The wax has a softening point of 86-88°C and rli!
The liquid in-service agent according to any one of claims 1 to 6, which is a hydrated castor oil having a concentration of 1+tlj2. 12. The wax has a softening point of about 70''C and an acid
The liquid in-service preparation according to any one of claims 1 to 4 JJI, which is polyoctadecene having hO. (3) 16. Carrier liquid with high recreational resistivity and low dielectric constant;
From pigments or dyes, N-vinylpyrrolidone-containing polymers, waxy substances and customary chilled mixtures, the pigments or &! A paste of the dye, N-vinylpyrrolidone-containing polymer and other additive mixture is cut into a form, this paste of raw material is ground at 60-100°C, and this ground material is added to the N-vinylpyrrolidone-containing polymer. By using a carrier α that can be bathed in a toner, this toner can be reduced by 5 to 20 times as much liquid as a liquid. When manufacturing a sample containing negatively charged toner particles for producing a material having a softening point mi!
It has J1150~120'C and R1 degree O~200, and in the carrier α body, it is easy to bathe at high temperature, but it is difficult to bathe at Murosho, and it has a conductivity of liquid state. 14. A process for producing a liquid developer, characterized in that at least one stick of wax is added to the raw material paste, and its ground material is also treated with Etner. 14. Wax , in the form of subdivided solid particles or keys?
17. The method according to claim 16, wherein the IJA is dispersed in a liquid and added to the raw material paste. 15. The method of claim 16, wherein the wax is stirred into the toner concentrate in the form of a very hot solution in a carrier liquid.